Hydrocarbon conversion with silica chromium oxide catalysts



Patented Aug. 14, 1945 HYDROCARBON CONVERSION WITH SILICA CHROM'IUM OXIDE CATALYSTS Robert F. Ruthrufl, Chicago, Ill., assimor to Prooess Management Company,

a corporation of Delaware No Drawing. Original a v Serial N 337,627. 1)

Ino., New York,

ppllcation May 28, 1940, ivlded and this applies-1 tion July 29, 1941, Serial No. 404,511

6 Claims.

The present application is a divisional application of my co-pending application, Serial No. 337,627, filed May 28, 1940.

The present application relates to catalysts containing silica and chromium oxide, and is particularly concerned with a. method of preparmg such catalysts whereby the components are brought together free from deleterious foreign substances and in a state of aggregation which is favorable to the manifestation of their catalydai properties. The present application also relate: to the employment of such catalytic substances in hydrocarbon conversions of the dehydrogenatlng or aromatizing type.

so far as is known silica alone is without efiect as a dehydrogenation catalyst and silica co-preoipitated or impregnated with chromium oxide by blown methods is likewise either inactive or very slightly active. The successful method comprising the present invention differs from prior methods most obviously in that ethyl ortho-silicote is used to produce silica in the gel form, the interstitialpore surface of which is so desirable for catalytic purposes providing it can be obtained free of deleterious substances.

Ethyl ortho-silicate is miscible with alcohol but almost immiscible with water. it is miscible with alcohol containing a small amount of water, however, and in the presence of this water undergoes a slow hydrolysis reaction as a result of which. it becomes miscible with larger amounts oi water. -When additional water is then added the hydrolysis soon goes to completion with the lom'iatlon of a; gel silica and ethyl alcohol. It will be seen that this is a method of obtaining gel silica completely tree of adsorbed ions such as. sodium and chloride ions. These and other ions have been shown to inhibit catalytic activity, and when silica gel is prepared by conventional methods involving the neutralization of water glass with an acid, it is doubtful whether all ions are completely removed even by prolonged washing. Thus it may be postulated that the superiority of the silica-chromium. oxide catalysts prepared by my method is due to the complete absence of foreign ions. Other explanations are possible, however, and it is to be understood that my invention is not limited by any theory advanced to account for its utility. The data hereinafter given establish the efficacy of my method beyond peradventure. v

In accordance with the method oi my invention, ethyl ortho-silicate is caused to hydrolyze bythe previously described procedure in the presence of hydrous chromium sesquioxide (Cram) which has been well washed to remove foreign ions, or in the presence of chromium trioxide (which yields the sesquioxide upon strong heating or reduction) which has been dissolved in the water causing the hydrolysis. When the sesquioxide is used directly, I allow an ethyl orthosilicate solution to {hydrolyze and precipitate silica thereon and therein, removing the residual liquid by decantation. In the case of the ethyl orthosilicate-chromium trioxide solution hydrolysis, I evaporate the solution as hydrolysis is taking place so that the chromium trioxide will be left on and in the precipitated silica.

These two variations difier in the order in which the two components are formed. In the first or sesquioxide variation, the chromium is precipitated first and the hydrolysed silica deposited on and in it." In the second or trioxide variation the hydrolysis takes place first with the deposition of chromium trioxide ((2103) in and on the silica,

and with the'subsequent conversion of the former into sesquioxide Both variations give an active catalyst, the first being preferred.

Two examples will now be given to illustrate how the catalyst may be prepared. In the first example, corresponding to the first variation mentioned in the previous paragraph, hydrous chromium sesquioxlde was prepared as follows:

Example I A 0.2 normal solution (based on the nitrate radical) oi chromium nitrate was made up by dissolving 152.4 grams of the nonahydrate Cr(NOa) 3.9H2O in 6 liters of water. An ammonia solution of the same normality was prepared by diluting 77 cc. of concentrated (29%) ammonium hydroxide with 6 liters of water. The chromium nitrate solution was rapidly stirred and the ammonia solution was added dropwise at a rate of d cc. per minute until 3 liters had been added.

elatinous precipitate was allowed to settle and the supernatant liquid was removed as combletely as possible, following which sufiicient distil ed Water was added to bring the volume up to of lower molecular weight hydrocarbons into olefins. They are especially satisfactory for preparing a high octane motor fuel from naphtha cipitate as a sludge after decantation of the last wash water. It will be observed that this method involves only the ammonium and nitrate ions, both of which are destroyed by heating.

To 300 cc; of ethyl ortho-silicate was added 1'75 cc. of ethyl alcohol andv 5.6 cc. of water.

The mixture was allowed to stand for 24 hours to allow hydrolysis to begin and was then diluted with sufilcient water to equal the volume of the last wash water removed from the chromium precipitate. The diluted silicate mixture was added to the chromium precipitate and stirred for four hours. After standing overnight to permit complete hydrolysis and precipitation of silica on and in the chromium sesquioflde, the

supernatant liquid was drawn oil and the catalyst filtered and dried.

grams of the catalyst prepared as above was placed in a tube; Normal heptane was then vaporized at the rate of 18 cc. per hour and passed through the tube, the catalyst and heptane vapors being contacted at a temperature of 890 F. The' conversion products were cooled to room temperature and separated into a liquid and a gas. 'In five hours the gas production amounted to a total of 15,350 ccs. of which more than 85% was hydrogen, while the liquid product was d to contain about 12% toluene. In a subsetuflnt run using 10 cc. of catalyst, butane was converted at the rate of8 liters per hour and at a temperature of 890 F. The C4 fraction of the product was found to contain about 11% olefins.

- Example II The second example to be given corresponds 40 finally the silica impregnated with CrOa was placed in a muilie furnace and heated to 1200 F. for one hour to convert the CrOrinto Cl'zOs. Treatmentwith a reducing agent such as alcohol may be substituted for the heating step if desired: for example, by boiling in dilute alcohol under a reflux condenser.

25 grams of the catalyst prepared as above was used to convert an East Texas heavy naphtha which was vaporized at the rate of 25 cc. per hour and contacted with it at 932 F. The conversion products were separated as in the previous runs and the gas evolved in fivehours, consisting of about 83% hydrogen, amounted to 7000 ccs.

By varying the proportions of the reagents from those takenv in the examples. I may obtain catalysts in which the ratio of chromium oxide to silica is any value desired, but in general the range of from 5 to 20% Crabs in the 7 final product is preferred. As shown by the examples, the catalysts prepared in accordance with my method, are-suitable for the conversion of hexanes and heptanes into the corresponding of low octane. In order to illustrate the unsuitability of chromium oxide-silica catalysts prepared by conventional methods for the aforementioned purposes, two additional examples will now be given.

Example III 100 grams of ordinary commercial grade silica gel purchased on the open market was added to 1000 ccspof water in which 20 grams of chromium trioxide had been dissolved. The solution was digested on a steam bath for two hours and the supernatant liquid then decanted. The silica was colored orange, indicating that impregnation had taken place. It was washed by dec'antation to remove superficial traces of the impregnating solution and was then placed in 1000 ccs. of water to which ccs. of ethyl alcohol had been added. The mixture was boiled under reflux with stirring for 16 hours, during which time the silica assumed a green color indiciating that the chromium trioxide had,

vaporized and passed over the catalyst at the rate of 25 ccs. (liquid volume) per hour, and 25 grams of catalyst was used in the test.

Example IV A chromium trioxide solution was made up by dissolving 45.7 grams in 250 cos. of water. A sodium silicate solution was made up by-dissolving 200 ccs. of a commercial grade known as "N Brand in 800 ccs. of water. 200 cos. of the chromium trioxide solution was then added to 500 ccs. oi the sodium silicate solution while stirring the latter-violently. A dark reddish gel was soon formed. Aiter the usual washing and drying operations this material was heated to- 1200 F. for one hour and then leached with water to remove NazO released as a product of the decomposition of sodium dichromatc into chromium sesquioxide. After redrying the material it was tested for catalytic activity by contacting it with vapors of an East Texas heavy naphtha exactly as in Example 11.. A very slight effect on the naphtha was observed, only 200 cos. of gas beingevolved in the first 30 minutes 0 operation.

Although the conditions of operation mentioned in the examples are suitable for determination of catalyst activity, in commercial operation I prefer to proceed differently. As already emphasized, the catalysts of my invention are or utility in the dehydro-aromatization of low oc tane naphthas for the production of high octane motor fuels. The process by which I bring this about is preferably operated at pressures between atmospheric and 500 pounds per square inch. I prefer to contact the naphtha vapors with the catalyst at temperatures of about 900'-to 1100' 1". for times'corresponding to space velocities-of cyclic compounds and for the dehydrogenation 7 about 0.1 to 10 liquid volumes of naphtha per aseasas per mol oi naphtha being converted, as this tends to retard the deposition of carbon on the catalyst.

The catalysts prepared in accordance with my invention are susceptible o1 repeated regeneration by the usual combustion methods when their activity has been impaired by the accumulation of a deposit of carbon.

My invention is not limited by the examples which have been given but only by and in the following claims in which I wish to claim all novel features residing therein.

I claim:

1. A method of dehydrogenating hydrocarbons which comprises-contacting vaporized hydrocarbons at elevated temperatures with a catalyst pors with a catalyst, said catalyst having been prepared by a method including the steps of hydrolyzing ethyl ortho-silicate in the presenceor an oxide of chromium. Y

2. In a method of dehydrogenating hydrocarbons involving the contacting of vaporized hydrocarbons at elevated temperatures with a catalyst, the improvement which comprises employing a catalyst prepared by hydrolyzing ethyl orthosilicate in the presence of chromium sesquioxide.

3. A method or preparing a high octane motor fuel from petroleum naphtha which comprises vaporizing said naphtha and contacting the vaproduced by a method including the hydrolysis of ethyl ortho-silioate. with a water solution of chromium trioxide and the conversion of chromium trioxide in the thus-produced silica gel into chromium sesquioxide.

4. In a method of dehydrogenating hydrocarbons involving the contacting of vaporized hydrocarbons with a catalyst at elevated temperatures. the improvement which comprises employing a catalyst prepared by hydrolyzing ethyl orthosilitaste in the presence of gelatinous chromium oxide.

5. In a method of dehydrogenating hydrocarbons involving the contacting of vaporized hydroca'rbons with a catalyst at elevated temperatures, the improvement which comprises employing a catalyst prepared, by hydrolyzing ethyl orthosilicate-in the presence of chromium trioxide and converting the said chromium trioxide to chromium sesquioxide.

6. A method of preparing'a high octane motor fuel from petroleum naphtha which comprises vaporizing said naphtha-and contacting the vapors with a catalyst, saidcatalyst having beenproduced by a method including the hydrolysis of ethyl orthosilicate in the presence of an oxide of chromium.

Roam'r r. 120mm; 

